EP0252592A1 - Halogenierte Diphenylätherderivate - Google Patents
Halogenierte Diphenylätherderivate Download PDFInfo
- Publication number
- EP0252592A1 EP0252592A1 EP87304449A EP87304449A EP0252592A1 EP 0252592 A1 EP0252592 A1 EP 0252592A1 EP 87304449 A EP87304449 A EP 87304449A EP 87304449 A EP87304449 A EP 87304449A EP 0252592 A1 EP0252592 A1 EP 0252592A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fluoro
- formula
- bromine
- bromo
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 0 *c(cc1Oc2ccccc2)ccc1F Chemical compound *c(cc1Oc2ccccc2)ccc1F 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
- C07C25/02—Monocyclic aromatic halogenated hydrocarbons
- C07C25/13—Monocyclic aromatic halogenated hydrocarbons containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/257—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings
- C07C43/29—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings containing halogen
Definitions
- This invention relates to novel halogenated diphenyl ethers, useful as intermediates in the preparation of insecticidal compounds, and to methods and intermediates for their preparation.
- the invention provides novel compounds of formula (I): wherein X is selected from bromine and chlorine.
- X is selected from bromine and chlorine.
- the specific compounds according to the invention are: 4-bromo-1-fluoro-2-phenoxybenzene, and 4-chloro-1-fluoro-2-phenoxybenzene
- the compounds of formula (I) are particularly useful as intermediates for the preparation of insecticides.
- UK Patent Specification No. 1,561,575 discloses the use of 1-bromo-3-phenoxybenzene as an intermediate in the preparation of insecticidally active alpha-trifluoromethyl-3-phenoxy-benzyl esters of carboxylic acids.
- Use of the compound of formula (I) wherein X is bromine in a manner analogous to that described in UK Patent Specification No. 1,561,575 provides alpha-trifluoromethyl-3-phenoxy-4-fluorobenzyl alcohol. This process is illustrated in Scheme I.
- the compound of formula (I) wherein X is bromine may also be used in the preparation of 4-fluoro-3-phenoxybenzaldehyde, a useful intermediate in the preparation of insecticidal compounds, for example 4-fluoro-3-phenoxybenzyl esters of cyclopropanecarboxylic acids and alpha-substituted derivatives thereof.
- One method of preparing 4-fluoro-3-phenoxybenzaldehyde follows the method of Olah and Arvanaghi, Angewandte Chemie, International Edition, 20 , p 878, 1981 and is illustrated in Scheme II.
- 4-Fluoro-3-phenoxybenzaldehyde may also be prepared from 4-bromo-1-fluoro-2-phenoxybenzene by the method of Einhorn and Luche, Tetrahedron Letters, 27 , p 1791, 1986, as illustrated in Scheme III:
- 4-Fluoro-3-phenoxybenzaldehyde is a useful intermediate in the preparation of 4-fluoro-3-phenoxybenzyl alcohol and its alpha-substituted derivatives, and insecticidal esters thereof.
- An example of its use is in the preparation of alpha-cyano-4-fluoro-3-phenoxybenzyl 3-(2-chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-dimethylcyclopropanecarboxylate, according to the method described in UK Patent Application No. 2,161,804A. This process is illustrated in Scheme IV.
- the compounds of formula (II) may be prepared from the compounds of formula (I) by the Heck reaction, using, for example, the method of Jeffery, Chemical Communications, 1984, p 1287.
- the invention provides a first process for preparing the compounds of formula (I), which comprises as a first step the diazotisation of 2-fluoro-5-haloanilines of formula (III): wherein X is selected from bromine and chlorine, followed by the addition of the resultant diazonium salt solution to a cooled solution of an alkali metal iodide, for example, potassium iodide.
- X is selected from bromine and chlorine
- the 4-halo-1-fluoro-2-iodobenzenes of formula (IV) are believed to be novel.
- the invention provides compounds of formula (IV), wherein X is selected from bromine and chlorine.
- the compounds of formula (I) wherein X is bromine may also be prepared from 4-fluoro-3-phenoxybenzaldehyde.
- the invention provides a second process for the preparation of the compounds of formula (I), in which 4-fluoro-3-phenoxybenzaldehyde is first oxidised to 4-fluoro-3-phenoxybenzoic acid, for example by the action of sodium periodate in the presence of ruthenium trichloride, using the method of Carlsen and Sharpless, Journal of Organic Chemistry, 46 , 3936, 1981. The acid is then converted to the acid chloride derivative using, for example, thionyl chloride.
- 4-Bromo-1-fluoro-2-phenoxybenzene may then be obtained from the acid chloride by reaction with bromotrichloromethane in the presence of an alkali metal salt of 2-pyridinethiol 1-oxide and a radical initiator using the method illustrated by Barton et al, Tetrahedron Letters, 24 , 4979, 1983; Tetrahedron Letters, 26 , 5939, 1985. This process is illustrated in Scheme VII.
- This Example illustrates the preparation of 4-bromo-1-fluoro-2-iodobenzene.
- a solution of sodium nitrite (1.71g) in water (4 cm3) was added dropwise to a stirred mixture of 5-bromo-2-fluoroaniline (4.5g), water (15 cm3), ice (15g) and concentrated sulphuric acid (1.8 cm3) at a temperature maintained at 0-5°C.
- the reaction mixture was stirred for 30 minutes, and further concentrated sulphuric acid (0.4 cm3) added.
- the resultant solution, containing 5-bromo-2-fluorobenzenediazonium sulphate was then added dropwise to a solution of potassium iodide (4.23g) in water (10 cm3) at a temperature of 5-6°C; vigorous effervescence was observed during the addition.
- This Example illustrates the preparation of 4-bromo-1-fluoro-2-phenoxybenzene.
- Cuprous chloride (0.452g) and a solution of 4-bromo-1-fluoro-2-iodobenzene (1.37g) in N,N-dimethylformamide (10 cm3) were added to the mixture, which was heated at 100°C for 17 hours; at this time, the reaction mixture was shown by gas liquid chromatography to contain only a small residue of the unreacted starting material.
- the mixture was cooled and extracted with diethyl ether. The extract was washed twice with water and once with brine, dried over anhydrous magnesium sulphate, filtered and concentrated by evaporation of the solvent under reduced pressure.
- the residual oil was passed through a short column of silica gel, using petroleum ether (boiling range 40-60°C) containing 10% by volume diethyl ether as eluent. Evaporation of the solvent under reduced pressure gave a clear, pale brown oil (0.92g). Distillation of this oil at reduced pressure (0.03 mmHg) yielded a number of fractions in a boiling range of 50-80°C. Two of these fractions were shown by thin layer chromatography to contain principally a single reaction product. These two fractions were combined and purified by preparative thin layer chromatography on a silica gel support, using petroleum ether (boiling range 40-60°C) as eluent.
- Infra red (liquid film) : 3100-3000, 3000-2800, 1600, 1495, 1450, 1405, 1275, 1250, 1220, 1190, 1170, 1120, 1075, 1025, 910, 880, 810, 755, 695, 630 cm ⁇ 1.
- this example illustrates the preparation of 4-fluoro-3-phenoxybenzoic acid.
- This Example illustrates the preparation of 4-fluoro-3-phenoxybenzoyl chloride.
- This Example illustrates the preparation of 4-bromo-1-fluoro-2-phenoxybenzene.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB868614002A GB8614002D0 (en) | 1986-06-09 | 1986-06-09 | Halogenated diphenyl ether derivatives |
GB8614002 | 1986-06-09 |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0252592A1 true EP0252592A1 (de) | 1988-01-13 |
Family
ID=10599186
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP87304449A Withdrawn EP0252592A1 (de) | 1986-06-09 | 1987-05-19 | Halogenierte Diphenylätherderivate |
Country Status (4)
Country | Link |
---|---|
US (2) | US4788349A (de) |
EP (1) | EP0252592A1 (de) |
JP (1) | JPS62292737A (de) |
GB (2) | GB8614002D0 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005077868A2 (de) * | 2004-02-16 | 2005-08-25 | Chiron As | Kongenere, chlorierte, bromierte und/oder iodierte, fluorierte aromatische verbindungen mit zwei benzolringen in ihrer grundstruktur, verfahren zu ihrer herstellung und ihre verwendung |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5283371A (en) * | 1986-03-13 | 1994-02-01 | National Research Development Corporation | Intermediates useful in the production of pesticides |
GB8814881D0 (en) * | 1988-06-22 | 1988-07-27 | Shell Int Research | Herbicidal acrylonitrile derivatives |
GB2241951A (en) * | 1990-03-16 | 1991-09-18 | Isc Chemicals Ltd | Chloro-difluorobenzenes and diazonium fluoborates |
JP6683693B2 (ja) * | 2014-10-14 | 2020-04-22 | シンジェンタ パーティシペーションズ アーゲー | ハロ置換ベンゼンを調製するプロセス |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3257471A (en) * | 1960-09-27 | 1966-06-21 | Douglas J Hennessy | Ddt derivatives |
EP0057384A2 (de) * | 1981-01-31 | 1982-08-11 | Bayer Ag | 4-Fluor-3-halophenoxy-benzylester, Verfahren zu deren Herstellung und deren Verwendung in Schädlingsbekämpfungsmitteln sowie neue Zwischenprodukte und Verfahren zu deren Herstellung |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2248488A (en) * | 1939-04-29 | 1941-07-08 | Dow Chemical Co | Nonflammable organic heat transfer agent |
US3950444A (en) * | 1973-03-05 | 1976-04-13 | Olin Corporation | Process for preparing ortho substituted aryl fluorides |
US4152455A (en) * | 1977-02-02 | 1979-05-01 | Fmc Corporation | Insecticidal α-trifluoromethyl-3-phenoxybenzyl carboxylates |
FR2456727A1 (fr) * | 1979-05-18 | 1980-12-12 | Rhone Poulenc Ind | Procede de preparation d'ethers diaryliques |
DE2933985A1 (de) * | 1979-08-22 | 1981-04-09 | Bayer Ag, 5090 Leverkusen | Neue 4-fluor-3-phenoxy-benzyl-ether und verfahren zu deren herstellung sowie neue zwischenprodukte hierfuer und verfahren zu deren herstellung |
DE3006685C2 (de) * | 1980-02-22 | 1982-09-09 | Riedel-De Haen Ag, 3016 Seelze | 3-Brom-4-fluorbenzonitril und Verfahren zur Herstellung eines substituierten 3-Brom-4-fluorbenzols |
FR2503698A1 (fr) * | 1981-04-08 | 1982-10-15 | Rhone Poulenc Spec Chim | Procede d'isomerisation de dichlorobromobenzenes |
DE3141659A1 (de) * | 1981-10-21 | 1983-05-05 | Bayer Ag, 5090 Leverkusen | Verfahren zur herstellung von in o-stellung substituierten fluoraromaten |
DE3200431A1 (de) * | 1982-01-09 | 1983-07-21 | Bayer Ag, 5090 Leverkusen | Verfahren zur herstellung von 4-fluor-3-phenoxytoluol |
FR2539411B2 (fr) * | 1983-01-17 | 1986-04-25 | Roussel Uclaf | Nouveaux derives de l'acide cyclopropane carboxylique, leur procede de preparation, leur application a la lutte contre les parasites |
DE3301868A1 (de) * | 1983-01-21 | 1984-07-26 | Bayer Ag, 5090 Leverkusen | Kernhalogenierte 3-fluortoluole und verfahren zu ihrer herstellung |
DE3520316A1 (de) * | 1985-06-07 | 1986-12-11 | Riedel-De Haen Ag, 3016 Seelze | Verfahren zur kontinuierlichen herstellung eines kernfluorierten aromatischen kohlenwasserstoffes |
JP2579310B2 (ja) * | 1986-03-13 | 1997-02-05 | ブリティッシュ・テクノロジー・グループ・リミテッド | 殺虫剤製造用中間体 |
US4730046A (en) * | 1986-04-14 | 1988-03-08 | Stauffer Chemical Company | Preparation of aryl halides |
JPH114921A (ja) * | 1997-06-13 | 1999-01-12 | Kawano:Kk | アイアン用ゴルフクラブヘッド |
-
1986
- 1986-06-09 GB GB868614002A patent/GB8614002D0/en active Pending
-
1987
- 1987-05-19 GB GB8711749A patent/GB2191484B/en not_active Expired - Fee Related
- 1987-05-19 EP EP87304449A patent/EP0252592A1/de not_active Withdrawn
- 1987-05-22 US US07/052,969 patent/US4788349A/en not_active Expired - Fee Related
- 1987-06-08 JP JP62141645A patent/JPS62292737A/ja active Pending
-
1988
- 1988-09-09 US US07/242,682 patent/US4870218A/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3257471A (en) * | 1960-09-27 | 1966-06-21 | Douglas J Hennessy | Ddt derivatives |
EP0057384A2 (de) * | 1981-01-31 | 1982-08-11 | Bayer Ag | 4-Fluor-3-halophenoxy-benzylester, Verfahren zu deren Herstellung und deren Verwendung in Schädlingsbekämpfungsmitteln sowie neue Zwischenprodukte und Verfahren zu deren Herstellung |
Non-Patent Citations (1)
Title |
---|
ANALYTICAL CHEMISTRY, vol. 33, no. 6, May 1961, pages 657,689,690; H.J. SLOANE: "Correlation of an infrared absorption band in the 10- to 11-micron region with the 3-substituted phenoxy group" * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005077868A2 (de) * | 2004-02-16 | 2005-08-25 | Chiron As | Kongenere, chlorierte, bromierte und/oder iodierte, fluorierte aromatische verbindungen mit zwei benzolringen in ihrer grundstruktur, verfahren zu ihrer herstellung und ihre verwendung |
WO2005077868A3 (de) * | 2004-02-16 | 2006-05-11 | Chiron As | Kongenere, chlorierte, bromierte und/oder iodierte, fluorierte aromatische verbindungen mit zwei benzolringen in ihrer grundstruktur, verfahren zu ihrer herstellung und ihre verwendung |
Also Published As
Publication number | Publication date |
---|---|
GB2191484A (en) | 1987-12-16 |
JPS62292737A (ja) | 1987-12-19 |
US4870218A (en) | 1989-09-26 |
GB2191484B (en) | 1990-05-02 |
US4788349A (en) | 1988-11-29 |
GB8614002D0 (en) | 1986-07-16 |
GB8711749D0 (en) | 1987-06-24 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE |
|
17P | Request for examination filed |
Effective date: 19880620 |
|
17Q | First examination report despatched |
Effective date: 19890711 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 19891122 |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: WHITTLE, ALAN JOHN |